This application claims priority to European Patent Application No. EP 01310795.8, filed Dec. 21, 2001, which is fully incorporated herein by reference.
This invention relates to a process for the manufacture of silicoaluminophosphate molecular sieves.
Silicoaluminophosphate (SAPO) molecular sieves are described in U.S. Pat. No. 4,440,871. These molecular sieves are generally classified as being microporous materials containing 8, 10 or 12-membered ring structures. These ring structures can have an average pore size ranging from about 3.5 xc3x85 to 15 xc3x85. Small pore SAPO molecular sieves with an average pore size from about 3.5 xc3x85 to 5 xc3x85 are typical of molecular sieves containing 8-membered rings.
An important use of SAPO is the catalytic conversion of oxygenates, e.g., methanol, to olefins, especially the lighter olefins, e.g., ethylene and propylene. The global demand for ethylene and propylene is increasing and as the cost of petroleum feedstock, their traditional source, increases, the use of SAPO catalysts in oxygenate to olefin conversion has significant commercial value. Numerous references, including U.S. Pat. No. 4,499,327 and EP-A-541,915, describe the manufacture of olefins from methanol using various SAPO molecular sieve catalysts. The literature describes a number of different processes for the manufacture of SAPO""s, in particular for the formation of the synthesis mixture which is to be subjected to the hydrothermal treatment typically used for the formation of the crystalline molecular sieves. In many such processes, the source of aluminium is added to an aqueous solution of the source of phosphorus, which is conveniently a strong phosphoric acid solution. The aluminium source is peptized by the phosphoric acid, a reaction that is hard to control, and results in a pasty composition difficult to handle, especially on a commercial scale.
Although the commercially most economic sources of aluminium are inorganic, many of these, for example hydrated aluminas, e.g., pseudoboehmite, have the disadvantage of not being readily soluble in water, tending to form a gel, which is also difficult to handle on a commercial scale. Although in principle these difficulties may be overcome, for example by the use of larger quantities of water, this dilutes the phosphoric acid and inhibits the process of digestion of the aluminium source.
If SAPO molecular sieves are to be used commercially, an economically acceptable way of preparing these materials in high yield and large quantities is needed. It is highly desirable that the structural and chemical properties of the product be consistent from one batch to another. The formation of an inconsistent process mixture or gel will interfere with preparing SAPO with consistent properties.
The present invention provides a process for the manufacture of a silicoaluminophosphate molecular sieve, which comprises forming a synthesis mixture by the steps of:
a) mixing an inorganic source of aluminium and water to form a mixture having a water to aluminium, measured as Al2O3, ratio within the range of 3:1 to 8:1 by weight;
b) mixing a source of phosphorus with the product of step a);
c) mixing a structure directing agent and a source of silicon with the product of step b); and
d) subjecting the synthesis mixture resulting from step c) to hydrothermal treatment under conditions effective to produce the desired silicoaluminophosphate molecular sieve.
Advantageously, the H2O:Al2O3 weight ratio of the mixture formed in step a) is within the range 3.5:1 to 6:1.
The components of the synthesis mixture are typically those known in the art or as described in the literature for the production of the SAPO concerned.
The aluminium source may be, for example, an aluminium oxide (alumina), optionally hydrated, an aluminium salt, especially a phosphate, an aluminate, or a mixture thereof. A preferred source is a hydrated alumina, most preferably pseudoboehmite, which contains about 75% Al2O3 and 25% H2O by weight.
Advantageously, the source of phosphorus is a phosphoric acid, especially orthophosphoric acid, but other sources, for example, organic phosphates, e.g., triethyl phosphate, and aluminophosphates may be used.
Advantageously, the source of silicon is silica, for example colloidal silica, famed silica, or an organic silicon source, e.g., a tetraalkyl orthosilicate, especially tetraethyl orthosilicate.
The synthesis mixture also contains a structure directing agent, or template. In general, these are organic bases, especially nitrogen-containing bases, more especially amines and quaternary ammonium compounds, used singly or in combinations. The template is chosen according to the SAPO being manufactured.
As templates there may be mentioned, for example, tetraethyl ammonium compounds, cyclopentylamine, aminomethyl cyclohexane, piperidine, triethylamine, cyclohexylamine, trimethylhydroxyethylamine, morpholine, dipropylamine (DPA), pyridine, isopropylamine and mixtures thereof. Preferred templates are triethylamine, cyclohexylamine, piperidine, pyridine, isopropylamine, tetraethyl ammonium compounds, dipropylamine, and mixtures thereof. The tetraethylammonium compounds include tetraethyl ammonium hydroxide (TEAOH), and tetraethyl ammonium phosphate, fluoride, bromide, chloride, and acetate. Preferred tetraethyl ammonium compounds are the hydroxide and the phosphate. The molecular sieve structure may be effectively controlled using combinations of templates.
Optionally, seeds of the desired SAPO or of a different molecular sieve, may be used to assist formation of the desired SAPO.
The process of the invention is suitable for the manufacture of, inter alia, SAPO-5, -8, -11, -16, -17, -20, -31, -36, -37, -40, -41, -42 and -47, especially suitable for the manufacture of SAPO-35, -44 and -56, and more especially suitable for the manufacture of SAPO-18 and SAPO-34, or more generally materials of the CHA or AEI structure types. The two last-mentioned SAPO""s may form as an intergrown material.
Substituted SAPOs may also be manufactured by the process of the invention. These materials are generally known as metal-containing silicoaluminophosphates or MeSAPOs. The metal may be an alkali metal (Group IA), alkaline earth metal (Group IIA), rare earth (Group IIIB, including the lanthanide elements) or the metals of Groups IB, IIB, IVB, VB, VIB, VIIB, and VIIIB. Preferably, Me represents Zn, Ni or Cu. These atoms may be incorporated into the tetrahedral framework through a MeO2 tetrahedral unit, typically by adding the metal component during synthesis of the molecular sieve.
The product of step a) of the process, which is generally a slurry, is advantageously mixed with the source of phosphorus by slowly adding the phosphorus source to the aluminium-containing product. However, the product may instead be slowly added to the phosphorus source. In either case, the addition is carried out at a rate sufficiently slow to prevent the formation of a viscous gel.
Admixture of the silicon source and the template then follow, being carried out in any conventional manner.
In general, the hydrothermal treatment of the synthesis mixture to yield the desired crystalline molecular sieve is advantageously carried out under autogenous pressure, for example in an autoclave, for example a stainless steel autoclave which may, if desired, be ptfe-lined. The treatment may, for example, be carried out at a temperature within the range of from 50, advantageously from 90, especially 120, to 250xc2x0 C., depending on the molecular sieve being made. The treatment may, for example, be carried out for a period within the range of from 20 to 200 hours, preferably up to 100 hours, again depending on the molecular sieve being formed. The procedure may include an ageing period, either at room temperature or, preferably, at a moderately elevated temperature, before the hydrothermal treatment at more elevated temperature. The latter may include a period of gradual or stepwise variation in temperature.
The treatment may be carried out with the vessel static or, preferably, with stirring or with rotating the vessel about a horizontal axis (tumbling). If desired, the synthesis mixture may be stirred or tumbled during an initial part of the heating stage, for example, from room temperature to an elevated, e.g., the final treatment, temperature, and be static for the remainder. Agitation generally produces a product with a smaller particle size and a narrower particle size distribution than static hydrothermal treatment.
A synthesis mixture for producing SAPO-34 according to the invention advantageously has a molar composition, apart from seeds if present, within the following ranges:
together with an organic template, advantageously tetraethylammonium hydroxide (TEAOH), dipropylamine (DPA), isopropylamine or morpholine, or a mixture of two or more such templates, in a proportion appropriate to yield SAPO-34. A preferred template mixture comprises TEAOH and DPA.
The invention also provides the use of forming an initial mixture of water and an inorganic aluminium source in a weight ratio of water to aluminium, calculated as Al2O3, within the range of 3:1 to 8:1 to facilitate handling of a silicoaluminate molecular sieve synthesis mixture.
The invention further provides the products of the process and of the use of the invention. The products, if required after cation exchange and/or calcining, have utility as catalyst precursors, catalysts, and separation and absorption media. They are especially useful in numerous hydrocarbon conversions, separations and absorptions. They may be used alone, or in admixture with other molecular sieves, in particulate form, supported or unsupported, or in the form of a supported layer, for example in the form of a membrane, for example as described in International Application WO 94/25151. Hydrocarbon conversions include, for example, cracking, reforming, hydrofining, aromatization, oligomerisation, isomerization, dewaxing, and hydrocracking (e.g., naphtha to light olefins, higher to lower molecular weight hydrocarbons, alkylation, transalkylation, disproportionation or isomerization of aromatics). Other conversions include the reaction of alcohols with olefins and the conversion of oxygenates to hydrocarbons, especially of methanol to olefins, especially light olefins. SAPO-34 produced by the process of the invention is especially suitable for this conversion.
Conversion of oxygenates may be carried out with the oxygenate, e.g., methanol, in the liquid or, preferably, the vapour phase, in batch or, preferably, continuous mode. When carried out in continuous mode, a weight hourly space velocity (WHSV), based on oxygenate, of advantageously 1 to 1000, preferably 1 to 100, hourxe2x88x921 may conveniently be used. An elevated temperature is generally required to obtain economic conversion rates, e.g., one between 300 and 600xc2x0 C., preferably from 400 to 500xc2x0 C., and more preferably about 450xc2x0 C. The catalyst may be in a fixed bed, or a dynamic, e.g., fluidized or moving, bed.
For the conversion of oxygenates, the SAPO, advantageously SAPO-34, advantageously has a relatively low SiO2:Al2O3 ratio, to minimize saturates formation. Advantageously a SiO2:Al2O ratio of at most 0.4:1, preferably at most 0.32:1 and most preferably at most 0.2:1 is employed.
The oxygenate feedstock may be mixed with a diluent, inert under the reaction conditions, e.g., argon, nitrogen, carbon dioxide, hydrogen, or steam. The concentration of methanol in the feedstream may vary widely, e.g., from 5 to 90 mole per cent of the feedstock. The pressure may vary within a wide range, e.g., from atmospheric to 500 kPa.